Zinc Hydrazides and Hydrazide‐Alkoxides with Cyclic and Acyclic Hydrazide Substituents

Abstract

AbstractThe tetrameric organometallic zinc hydrazides the {(RZn)4[NHN(CH2)n]4} (R = Me, Et, iPr and n = 5, 4) (1–6), were prepared by alkane elimination from dialkyl zinc solutions and the ring‐substituted hydrazine derivatives 1‐aminopiperidine and 1‐aminopyrrolidine at ambient temperature. They were characterized by NMR (1H, 13C) and IR spectroscopy, by mass spectrometry and by elemental analyses. The compounds form asymmetric aggregates, containing Zn4N8 cores. Zinc trisalkoxide‐monohydrazides can be prepared in one‐pot syntheses by reacting dialkylzinc solutions simultaneously with alcohols and hydrazines. Reactions of dimethylzinc with isopropanol and monomethylhydrazine or mono‐t‐butylhydrazine in 2:1:1.03 ratio resulted in the formation of [(MeZn)4(NHNHR)(OiPr)3] [R = Me (7), tBu (8)]. In a similar fashion, dialkylzinc compounds react with 1‐aminopiperidine and alcohol in 5:4:4 ratio to give {(RZn)4[NHN(CH2)5](OR′)3]} [R = Me, R′ = iPr (9); R = Et, R′ = Et (10), iPr (11)]. These compounds were characterized as the above compounds. The structures of compounds 8 and 9 were also determined by crystal structure analyses. These compounds show an unsymmetrical aggregation with a Zn4N2O3 cage structure, confirmed by spectroscopic methods in solution.